EP0236701B1 - Verbessertes Verfahren zur Wiederaufarbeitung Kohlennstoff enthaltender Abfälle - Google Patents

Verbessertes Verfahren zur Wiederaufarbeitung Kohlennstoff enthaltender Abfälle Download PDF

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Publication number
EP0236701B1
EP0236701B1 EP87100875A EP87100875A EP0236701B1 EP 0236701 B1 EP0236701 B1 EP 0236701B1 EP 87100875 A EP87100875 A EP 87100875A EP 87100875 A EP87100875 A EP 87100875A EP 0236701 B1 EP0236701 B1 EP 0236701B1
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Prior art keywords
hydrogen
bars
hours
waste
minute
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German (de)
English (en)
French (fr)
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EP0236701A1 (de
Inventor
Joachim Dr. Korff
Axel Dr. Giehr
Karl-Heinz Keim
Kurt Erdt
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RWE Entsorgung AG
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RWE Entsorgung AG
Rheinische Braunkohlenwerke AG
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Priority to AT87100875T priority Critical patent/ATE53859T1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/18—Treating trash or garbage

Definitions

  • the invention relates to a process for the reprocessing of carbon-containing waste by thermal pretreatment of the same in the presence or absence of hydrogen and subsequent hydrogenation of the pretreated material at elevated temperature and at least 200 bar hydrogen pressure.
  • Waste has been used in landfills for decades, e.g. stored in abandoned gravel pits, mine pits and elsewhere. For a long time, the chemical structure of the waste and its long-term effects on soil and groundwater have not been taken into account. More recently, certain types of waste have been dumped in so-called special landfills. Here, efforts are made to seal the landfill from groundwater and soil.
  • This invention relates to hydrogenation treatment with or without catalyst, synthetic waste materials such as e.g. Plastics or Kungstoffgemischen, rubber, waste tires, textile waste, chemical industrial waste, waste oils, waste oils and other or mixtures of these materials, the hydrogenating treatment at pressures from 30 to 500 bar, preferably from 50 to 450 bar and particularly preferably from 50 to 350 bar is carried out and at temperatures from 200 to 600 ° C, preferably from 200 to 540 ° C and particularly preferably from 300 to 540 ° C and residence times from 1 minute to 8 hours, preferably from 10 minutes to 6 hours and particularly preferably from 15 Minutes to 4 hours.
  • synthetic waste materials such as e.g. Plastics or Kungstoffgemischen, rubber, waste tires, textile waste, chemical industrial waste, waste oils, waste oils and other or mixtures of these materials
  • Rubbing oils can be added to the waste feed products as well as coal, coal components, crude oil, crude oil components and crude oil residues, shale oils and shale oil components, oil sand extracts and their components, bitumen, asphalt, asphaltenes and similar materials.
  • the feed product or the feed mixture can also be treated with solvents and the extract can then be used in the hydrogenating treatment.
  • the process allows the synthetic waste materials to be converted into valuable hydrocarbons without further separation.
  • gases gaseous C, -C 4 hydrocarbons, liquid hydrocarbons in the naphtha boiling range as well as middle distillates and heavy oils, which are used as heating oils or diesel power fabric can be used.
  • the pre-sorting of waste materials is preferably carried out in such a way that carbon-containing organic waste of synthetic origin such as plastics and mixtures of plastics, rubber, waste tires, textile waste or mixtures of these materials and further organic synthetic waste are at least roughly separated from vegetable waste and / or biomass are then subjected to a hydrogenating treatment or the same in a mixture with organic industrial waste of synthetic origin such as paint and paint residues, organic chemicals, waste from industrial plants, organic synthetic shredder waste from the automotive industry, sewage sludge, waste oils or other industrial organic waste of synthetic origin from the hydrogenation be subjected.
  • organic industrial waste of synthetic origin such as paint and paint residues, organic chemicals, waste from industrial plants, organic synthetic shredder waste from the automotive industry, sewage sludge, waste oils or other industrial organic waste of synthetic origin from the hydrogenation be subjected.
  • waste materials such as paper, food scraps, agricultural and forestry waste, plant residues and others can be roughly separated or remain to some extent in the synthetic portion.
  • Household waste can be processed, for example, by roughly separating plastics, rubber, textiles and other synthetic materials and separately subjecting them to a hydrogenation treatment, or mixed with waste tires and / or industrial chemicals and / or plastic waste and / or waste oils and others be subjected to this hydrating treatment.
  • Werwer is also very well suited for the hydrating treatment of the waste or waste mixtures mentioned in combination with coal, coal components such as residual oils from coal, coal oils, pyrolysis oils, crude oil, residual oils from crude oil, other crude oil components, oil shale and oil shale components, oil sand extracts, asphalt and Bitumen and similar materials as well as with mixtures of the materials mentioned.
  • coal components such as residual oils from coal, coal oils, pyrolysis oils, crude oil, residual oils from crude oil, other crude oil components, oil shale and oil shale components, oil sand extracts, asphalt and Bitumen and similar materials as well as with mixtures of the materials mentioned.
  • the separation of the above-mentioned inorganic materials from the carbon-containing waste can be carried out according to the prior art. These inorganic materials can be stored in landfills provided they are not recycled and reprocessed. The crushing and shredding and separation of waste materials can also be carried out according to the prior art. If this is not contradicted by equipment, the process can also be carried out in the presence of inorganic materials.
  • Waste components that cannot be converted to hydrocarbons such as sulfur, nitrogen, oxygen and halogens in the form of their compounds, are converted into their gaseous hydrogen compounds, namely H 2 S, NH 3 , HCl, H 2 0 and others. These compounds can be separated by gas washing and further work-up according to the prior art.
  • Another advantage of the process is that the formation of hazardous compounds that occur during waste incineration, namely NO X , SO. or dioxins is avoided. Furthermore, plastics, such as polyvinyl chloride, which are problematic in combustion, can be processed without risk to the environment.
  • the hydrogenation of carbon-containing waste materials can, according to this disclosure, be carried out with very good results in the absence of catalysts. However, improved results, particularly with regard to the selective formation of certain hydrocarbon fractions, can be obtained in the presence of catalysts, e.g. in the presence of metals and their compounds which are catalytically active in hydrogenation reactions, e.g.
  • catalysts can consist of a single active component or a mixture of at least 2 of the components mentioned, and wherein these metals or their compounds can be applied to catalyst supports, such as on aluminum oxide, silicon oxide, aluminum silicate, zeolites and other supports which are known from the prior art, as well as on mixtures of these supports or also without a support. Certain zeolites and other carriers are also active as catalysts in the disclosed process without doping.
  • Suitable catalysts are so-called disposable catalysts such as hearth furnace coke, gasification dusts and ashes such as, for example, high-temperature Winkler dust and ashes, dusts and ashes which are obtained in the hydrogenating gasification of coal, in which methane is formed (HKV dust), and materials that contain iron oxides such as red mud, Bayer mass, Lux mass, dusts from the steel industry and others.
  • gasification dusts and ashes such as, for example, high-temperature Winkler dust and ashes, dusts and ashes which are obtained in the hydrogenating gasification of coal, in which methane is formed (HKV dust)
  • materials that contain iron oxides such as red mud, Bayer mass, Lux mass, dusts from the steel industry and others.
  • These materials can be used as such as catalysts or doped with metals and / or metal compounds which are active in hydrogenations, in particular with heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd, also alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.
  • heavy metals and / or their compounds such as Fe, Cr, Zn, Mo, W, Mn, Ni, Co, Pt , Pd
  • alkali and alkaline earth metals or their compounds such as Li, Na, K, Rb, Be, Mg, Ca, Sr or Ba and mixtures of these metals and / or their compounds.
  • the catalysts can optionally be sulfided before or during the process.
  • All catalysts can be used as individual components or in a mixture of at least two of the components.
  • the hydrating treatment can be carried out within wide limits of temperature and pressure, depending on the waste material used, namely from 200-600 ° C. and 30-500 bar, with residence times of 1 minute to 8 hours.
  • the hydrogenation gas can be of different quality, for example it can contain certain amounts of CO, CO 2 , H 2 S, methane, ethane, steam and others in addition to hydrogen.
  • Suitable hydrogen qualities are, for example, those obtained when gasifying carbon-containing materials.
  • Such materials can be residues from mineral oil processing or other oils or hydrocarbons from mineral oil origin, or coal such as lignite, but also hard coal, wood, peat or residues from coal processing such as coal hydrogenation.
  • Suitable gasification materials are also biomass and the vegetable portion of household waste.
  • pure hydrogen qualities such as those obtained electrolytically: are also very suitable.
  • Household waste can accordingly be processed in such a way that a separation into a vegetal and a synthetic part takes place and then the vegetable part is gasified to provide hydrogen in the hydrogenation process, while the synthetic part is treated with hydrogen.
  • treatment with suitable solvents is also possible, in particular with hydrogen-transferring solvents, this treatment being carried out before the actual hydrogenation.
  • dissolved and undissolved material can be separated from one another and subjected separately to a hydrogenation, or dissolved and undissolved material can be reacted together in a reactor in a hydrogenating manner.
  • the solvent can be separated off and recycled by subsequent distillation.
  • the undissolved material can be subjected to gasification or coking.
  • the waste material used can be mixed with coal and coal components, crude oil and crude oil components and other similar materials, as already explained above.
  • Suitable hydrogen-transferring solvents are, for example, tetralin, anthracene oil, isopropanol, oils containing cresols, decalin, naphthalene, tetrahydrofuran, dioxane and other hydrocarbons from crude oil and coal or hydrocarbons which originate from the process itself, and also oxygen-containing hydrocarbons and oils.
  • water and steam can also be added, the latter also being able to be added to the alternative hydrogenating treatments already explained above.
  • the waste material can first be separated into a vegetable, biomass or cellulose portion and a synthetic portion, both portions being further processed separately, and the vegetable, biomass or cellulose portion being essentially hydrolytically split, for example in the presence of bases or acids, this conversion preferably being carried out in the presence of protic solvents, in particular water and alcohols, and / or in the presence of carbon monoxide and / or hydrogen and, on the other hand, the essentially proportion of the hydrogenating treatment described above.
  • the pretreatment according to the invention can be carried out in the presence of hydrogen and / or hydrogen-containing gases and / or hydrogen-transferring solvents, and also in Inert atmosphere or in solvents which are not considered. Hydrogen carriers work.
  • the process can also be carried out with or without catalysts.
  • extruders can be used, for example, with single or multiple screw conveyance or, for example, those as used for conveyance or, for example, those as described in DE-OS 30 01 318 or DE-OS 29 49 537, the latter in which the screw conveyor ( n) protrudes (s) behind the actual conveying section into an enlarged reaction space, so that additional mixing takes place through the screw (s).
  • kneading disc screw presses kneaders, hollow screw heat exchangers, screw kneaders, kneading extruders, stirring apparatuses, continuous mixers, kneaders, grinding devices or mills such as bead, hammer or vibrating mills
  • stirring apparatuses continuous mixers
  • kneaders stirred tanks, mills and the like
  • a feed extruder can optionally be connected downstream, which brings about a pressure increase up to the pressure of the hydrogenation reactor.
  • Apparatuses which are very suitable according to the invention are, in particular, those which simultaneously mix and knead.
  • the desired plasticization, dispersion, homogenization, degassing and degradation reaction takes place in a particularly suitable manner, which leads to the desired viscosities. It is known that the reaction rate can also be increased by improving the mixing.
  • the devices mentioned can optionally also be adapted to certain feedstocks, for example containing gas feeds, feed devices at different points on the pretreatment section, drying, heating and cooling sections, addition devices for liquid feed products and the like. Furthermore, several of the devices mentioned can be connected in series or in parallel so that a total of a feed mixture of the desired properties is present at the entrance of the hydrogenation reactor (s) downstream, in particular with regard to the degree of degradation and viscosity.
  • the devices mentioned are preferably selected from the point of view that a sufficient amount of hydrogen required for the reaction reaches the feedstock to be converted.
  • Suitable for this purpose are, for example, stirring devices, mixing / kneading devices, extruders or the devices disclosed in DE-OS 30 01 318 and DE-OS 29 43 537 or other of the devices mentioned can be used, if appropriate with appropriate feeds for hydrogen.
  • hydrogen can also be supplied upstream of the mixing device.
  • the hydrogenating treatment is carried out in the pretreatment device at a temperature of 75-600 ° C, preferably 75-540 ° C, particularly preferably 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar , particularly preferably from 1-350 bar and a residence time from 1 minute to 6 hours, preferably from 1 minute to 4 hours, the desired amount of hydrogen being able to be supplied in one or more stages, depending on the mixing device.
  • the thermal pretreatment is carried out in the mixing device at 75-600 ° C, preferably from 75-540 ° C, particularly preferably at 120-475 ° C, a pressure of 1-600 bar, preferably of 1-500 bar, particularly preferably of 1-350 bar and a residence time of 1 minute to 6 hours, preferably 1 minute to 4 hours.
  • the pretreatment according to the invention in particular in the case of thermal pretreatment, can also be carried out under a pressure lower than 1 bar.
  • inert gas can be introduced in one or more stages, depending on the mixing device used.
  • Inert gases can be, for example, nitrogen, carbon dioxide, steam, carbon monoxide, methane and other low-boiling hydrocarbons, as well as mixtures of these gases.
  • Hydrogen can also be present in small quantities. Small amounts of oxygen or air may also be permitted.
  • mixing devices for hydrogenating or thermal pretreatment can be combined in parallel connection or in series connection.
  • the gases mentioned can also be added before the actual pretreatment.
  • a hydrogen-transferring solvent or a mixture of such solvents can also be used as such or in combination with additional hydrogen or inert gas.
  • the hydrogenating pretreatment is carried out at a temperature of 75-600 ° C, preferably at 75-540 ° C and particularly preferably at 120-500 ° C, a pressure of 1-600 bar, preferably 1-500 bar and particularly preferably from 1-350 bar and a residence time of 1 minute to 6 hours, preferably from 1 minute to 4 hours.
  • the conversion in the mixing device can also be carried out in the presence of protic solvents, in particular in the presence of water or methanol and / or at least one component from the group: ethanol, C 3 -C 4 alcohols and higher alcohols.
  • Protic solvents at least partially lead to hydrolysis. If the reaction is carried out in the pretreatment mixing device, temperatures of 75-600 ° C are used, preferably 75-540 ° C and particularly preferably 120-500 ° C, pressures of 1-600 bar, preferably 1-500 bar, particularly preferably from 1-350 bar and residence times from 1 minute to 6 hours, preferably from 1 minute to 4 hours.
  • the hydrolysis can also be carried out in the presence of hydrogen, hydrogen-containing gases or hydrogen-transferring solvents with or without a catalyst or with or without CO. Typical hydrolysis catalysts, such as acids or bases including organic amines, can be used. The catalysts mentioned on pages 6 and 7 can also be included.
  • the pretreatment according to the invention can be carried out in the presence of solvents which do not have a hydrogen transfer effect, such as of aromatics such as benzene, toluene or the xylenes.
  • solvents which do not have a hydrogen transfer effect such as of aromatics such as benzene, toluene or the xylenes.
  • Non-aromatic solvents can also be used, such as saturated or substantially saturated aliphatic hydrocarbons in boiling ranges between, for example, 30 and more than 500 ° C.
  • the high-boiling fractions can, for example, be residual oils, as already mentioned above.
  • the hydrating cleavage in the pre-treatment device can be set to the desired extent, up to a breakdown as described in the hydrating treatment of waste according to DE-PS 34 42 506 or in the European subsequent application EP-A-182,309.
  • a downstream hydrogenation reactor can be dispensed with.
  • the hydrogenating pretreatment can be carried out with or without the catalysts which are disclosed on pages 6 and 7.
  • Catalysts can be introduced into the pretreatment device or added before it.
  • the waste from organic synthetic materials can be converted into liquid hydrocarbons which boil essentially in the naphtha or gasoline range or middle distillate range. Examples of such waste are disclosed on pages 3 and 4.
  • a particular advantage of the method according to the invention results from the fact that the conditions in the pretreatment device can be set so that a product is obtained which can be handled without problems in subsequent steps, e.g. can be pumped or conveyed via screw conveyors, whereby the conditions can be adapted to the type of waste used, which, as already mentioned above, plastic materials, paint residues, paint compositions, industrial chemicals such as those that have to be deposited in special landfills according to the prior art, shredder waste from the automotive industry, used lubricating oils, elastomers, textile materials but also to a certain extent paper, cardboard and other cellulose-containing materials such as wood waste, sawdust or vegetables from household waste.
  • the pretreated product can also be conveyed directly from the pretreatment device into the hydrogenation reactor, for example by means of an extruder.
  • the method according to the invention therefore also allows only a little pre-sorted waste to be implemented. However, for reasons of equipment, it is desirable to separate inorganic materials such as stones, metals, glass and others before the pretreatment, at least rough materials.
  • Vegetables can be processed separately, for example by fermentation.
  • An important advantage of the present invention results from the fact that the hydrogenating or thermal pretreatment according to the invention, in combination with the subsequent hydrogenation of the pretreated waste, means that even very inhomogeneous waste mixtures can be used as the feed product, these being converted into valuable liquid hydrocarbons in high yields.
  • the heteroatoms such as oxygen, sulfur, nitrogen or halogens, which are contained in many waste materials, are converted according to the invention into their hydrogen derivatives, which can be worked up further according to the prior art without any problems.
  • halogenated wastes are, for example, polychlorobiphenylenes, polyvinyl chloride, fluorine-containing polymers or halogens-containing solvents.
  • a particularly advantageous effect of the thermal or hydrogenating pretreatment is the result that, depending on the temperature, residence time and pressure, a large amount of halogens, essentially as hydrogen halides, is eliminated in the pretreatment.
  • a large amount of halogens essentially as hydrogen halides
  • about 90% of the halogen is already removed from waste containing polyvinyl chloride at 250 ° C., a residence time of 30 minutes and a hydrogen or nitrogen pressure of 10 bar or less as hydrogen chloride.
  • Halogen elimination can also be promoted by increasing the temperature and increasing the residence time. Halogen elimination can also be promoted by catalysts such as those mentioned on pages 6 and 7. Such catalysts which are used according to the prior art for the elimination of hydrogen halide, such as Friedel-Crafts catalysts and / or organic amines and / or other basic compounds, can also be used according to the invention. As a result, hydrogen halides can be split off even under mild conditions.
  • materials can also be added to the waste used, or added to the pretreatment device or the hydrogenation reactor, such as crude oil, crude components and products derived from crude oil, asphalts, bitumen, mineral tars, coal, coal components, products from coal, lignite, Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.
  • crude oil, crude components and products derived from crude oil, asphalts, bitumen, mineral tars, coal, coal components, products from coal, lignite, Peat, pyrolysis oils such as those obtained from coking processes or pyrolysis processes, oil sands, oil sand products, residual oils from crude oil processing, from cracking plants, vacuum residues, shale oils and shale oil products and similar materials.
  • a hydrolysis stage can precede the thermal or hydrogenating pretreatment.
  • the hydrolysis reaction is preferably carried out in a mixing device as described above, in the presence of protic solvents, in particular in the presence of water and / or methanol and / or at least one component from the group: ethanol, C 3 -C 4 alcohols and higher alcohols , at a pressure of 1-150 bar, preferably of 1-120 bar and a temperature of 50-300 ° C and preferably of 75-250 ° C. Lower pressures are preferred if the gases that are formed during the hydrolysis are to be removed from the hydrolysis device.
  • the hydrolysis stage can alternatively be switched between the pretreatment and the actual hydrogenation.
  • the hydrolysis conditions are preferably adapted to the temperature and the pressure in the pretreatment stage or hydrogenation stage or both.
  • vegetables and biomass can be hydrolytically split and separated from waste of synthetic organic origin.
  • the hydrolysis reaction can be accelerated by adding acids or bases in accordance with the prior art.
  • the hydrolytic reaction can also be carried out in the presence of hydrogen, hydrogen-containing gases, hydrogen-transferring solvents, catalysts as exemplified on pages 6 and 7 or solvents which are not suitable for mass transfer, or in the presence of inert gases.
  • grating oils are also added according to the invention in the pretreatment device or before or after this.
  • the grinding oils can originate from the process itself or can be of foreign origin.
  • metals or metal compounds which are present in the wastes can advantageously be worked up, since they occur in residues or ashes in a relatively high concentration after the hydrogenation. These residues or ashes can be worked up, for example, to obtain the pure metals.
  • Example 1 was repeated, but under a nitrogen pressure of 10 bar. In the case of the temperature of 300 ° C, an additional nitrogen pressure of 2 bar was used. The results are shown in Table 2.
  • a mixture of essentially synthetic waste from an industrial waste sorting plant which contained 10% by weight of polyvinyl chloride was mixed with a used lubricating oil in a waste to oil ratio of 1: 3, as described in Example 1 and at temperatures of 250 ° C., 300 ° C and 350 ° C treated for two hours at a pressure of 10 bar nitrogen or hydrogen.
  • a mixture of mineral residual oils and a waste mixture consisting of 10% by weight of old tires, 70% by weight of essentially synthetic-organic waste from a technical waste separation system and 20% by weight of polyvinyl chloride was mixed and kneaded at 350 ° C. for 20 minutes and 450 ° C treated with a hydrogen or nitrogen pressure of 200 bar.
  • the ratio of waste to oil was 1: 3.
  • FeS0 4 treated with NaOH was used as catalyst.
  • Waste that consisted mainly of organic synthetic material and a technical Waste sorting plant was obtained, with 15 wt.% Polyvinyl chloride, was treated in a mixer / kneader at 200 bar hydrogen and temperatures of 350 ° C and 470 ° C for 30 minutes. At the temperature of 350 ° C, an experiment was carried out with and without a catalyst. A nickel / molybdenum catalyst was used as the catalyst. No rubbing oil was used. The viscosities obtained are shown in Table 6.
  • Waste which consisted essentially of organic synthetic material from a technical waste separation plant and which contained 5% by weight of perfluorinated polyethylene (Teflon) and 20% by weight of textile waste made of 50% wool and 50% polyacrylonitrile was treated as described in Example 6.
  • the viscosities obtained are shown in Table 8.
  • the results according to the invention are of great importance for waste hydrogenation on an industrial scale, since the downstream hydrogenation reactors and other parts of the plant which are exposed to high pressures can be made from less valuable materials.
  • the process according to the invention is therefore of particular importance for waste feed materials which contain chlorinated constituents.
  • the examples also show that, under suitable conditions and conditions, increased degradation takes place under nitrogen compared to hydrogen.
  • the conditions of the pretreatment can be varied over a wide range of temperature, pressure and residence times, the conditions for the subsequent hydrogenation can also be varied over a wide range, the two treatments complementing one another.
  • the pretreatment according to the invention is carried out at a relatively high temperature and residence time or corresponding pressure, in particular at a relatively high hydrogen pressure
  • the subsequent hydrogenation can, depending on the product used, be carried out under relatively mild conditions. This applies in particular if the pretreatment has already led to extensive dismantling.
  • Both stages therefore complement one another in accordance with the invention and can be adapted excellently to the operational waste material as required.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Treating Waste Gases (AREA)
  • Hydrogen, Water And Hydrids (AREA)
EP87100875A 1986-01-24 1987-01-22 Verbessertes Verfahren zur Wiederaufarbeitung Kohlennstoff enthaltender Abfälle Expired - Lifetime EP0236701B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87100875T ATE53859T1 (de) 1986-01-24 1987-01-22 Verbessertes verfahren zur wiederaufarbeitung kohlennstoff enthaltender abfaelle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3602041 1986-01-24
DE3602041A DE3602041C2 (de) 1986-01-24 1986-01-24 Verbessertes Verfahren zur Aufarbeitung von Kohlenstoff enthaltenden Abfällen

Publications (2)

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EP0236701A1 EP0236701A1 (de) 1987-09-16
EP0236701B1 true EP0236701B1 (de) 1990-05-02

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EP87100875A Expired - Lifetime EP0236701B1 (de) 1986-01-24 1987-01-22 Verbessertes Verfahren zur Wiederaufarbeitung Kohlennstoff enthaltender Abfälle

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US (1) US4982027A (ja)
EP (1) EP0236701B1 (ja)
JP (1) JPS62253689A (ja)
CN (1) CN87101612A (ja)
AT (1) ATE53859T1 (ja)
AU (1) AU583704B2 (ja)
BR (1) BR8700298A (ja)
CA (1) CA1300540C (ja)
DD (1) DD261170A1 (ja)
DE (2) DE3602041C2 (ja)
ES (1) ES2000077B3 (ja)
GR (2) GR880300006T1 (ja)
IN (1) IN169120B (ja)
PL (1) PL263795A1 (ja)
ZA (1) ZA87408B (ja)

Cited By (3)

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EP0236701A1 (de) 1987-09-16
BR8700298A (pt) 1987-12-01
PL263795A1 (en) 1988-02-04
ES2000077B3 (es) 1990-08-16
JPS62253689A (ja) 1987-11-05
ZA87408B (en) 1987-08-26
DE3762522D1 (de) 1990-06-07
AU6809087A (en) 1987-08-06
CA1300540C (en) 1992-05-12
AU583704B2 (en) 1989-05-04
ES2000077A4 (es) 1987-11-16
DD261170A1 (de) 1988-10-19
DE3602041A1 (de) 1987-07-30
GR3000553T3 (en) 1991-07-31
US4982027A (en) 1991-01-01
IN169120B (ja) 1991-09-07
GR880300006T1 (en) 1989-06-22
ATE53859T1 (de) 1990-06-15
DE3602041C2 (de) 1996-02-29

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